KR20030066676A - Microbiocidal N-phenyl-N-[4-(4-pyridyl)-2-pyrimidin-2-yl]-amine derivatives - Google Patents

Abstract

The invention relates to novel N-phenyl-4-(4-pyridyl)-2-pyrimidineamine derivatives of the general formula (I) wherein the sum of (m+p) together is 0, 1, 2 or 3; n and q are independently of each other 0 or 1, and the sum of (m+p+q) together is 1, 2, 3 or 4; R<SUB>1 </SUB>is hydrogen, halogen, alkoxy, haloalkyl, haloalkoxy or alkyl; R<SUB>2 </SUB>is hydrogen, C<SUB>1</SUB>-C<SUB>6</SUB>-alkyl, C<SUB>1</SUB>-C<SUB>6</SUB>-haloalkyl or C<SUB>1</SUB>-C<SUB>6</SUB>-alkoxy; R<SUB>2A </SUB>is hydrogen, C<SUB>1</SUB>-C<SUB>6</SUB>-alkyl, C<SUB>3</SUB>-C<SUB>4</SUB>-alkenyl or C<SUB>3</SUB>-C<SUB>4</SUB>-alkynyl; each of R<SUB>3</SUB>, R<SUB>4</SUB>, R<SUB>5 </SUB>and R<SUB>6 </SUB>is, independently of the others, hydrogen, C<SUB>1</SUB>-C<SUB>6</SUB>-alkyl, C<SUB>1</SUB>-C<SUB>6</SUB>-haloalkyl, hydroxy-C<SUB>1</SUB>-C<SUB>6</SUB>-alkyl or C<SUB>1</SUB>-C<SUB>6</SUB>-alkoxy-C<SUB>1</SUB>-C<SUB>6</SUB>-alkyl, or the ring members CR<SUB>3</SUB>R<SUB>4 </SUB>or CR<SUB>5</SUB>R<SUB>6 </SUB>or CR<SUB>2</SUB>R<SUB>2A </SUB>are independently of each other a carbonyl group (C-O) or a group C-S; X is C-O, C-S, S-O or O-S-O; Y is O, S, C-O, CH<SUB>2</SUB>, -N(R<SUB>8</SUB>)-, -O-N(R<SUB>8</SUB>)-, -N(R<SUB>8</SUB>)-O- or NH-; R<SUB>7 </SUB>is hydrogen, C<SUB>1</SUB>-C<SUB>4</SUB>-alkyl, C<SUB>3</SUB>-C<SUB>4</SUB>-alkenyl, C<SUB>3</SUB>-C<SUB>4</SUB>-alkynyl, -CH<SUB>2</SUB>OR<SUB>8</SUB>, CH<SUB>2</SUB>SR<SUB>8</SUB>, -C(O)R<SUB>8</SUB>, -C(O)OR<SUB>8</SUB>, SO2R<SUB>8</SUB>, SOR<SUB>8 </SUB>or SR<SUB>8</SUB>; and R<SUB>8 </SUB>is C<SUB>1</SUB>-C<SUB>8</SUB>-alkyl, C<SUB>1</SUB>-C<SUB>8</SUB>-alkoxyalkyl, C<SUB>1</SUB>-C<SUB>8 </SUB>haloalkyl or phenylC<SUB>1</SUB>-C<SUB>2</SUB>-alkyl wherein the phenyl may be substituted by up to three groups selected from halo or C<SUB>1</SUB>-C<SUB>4</SUB>-alkyl; or a salt thereof. The invention also relates to the preparation of the compounds and to agrochemical compositions comprising at least one of those compounds as active ingredient as well as the preparation of the said compositions and to the use of the compounds or of the compositions in controlling or preventing the infestation of plants by phytopathogenic microorganisms, especially fungi.

Description

Microbial N-phenyl-N- [4- (4-pyridyl) -2-pyrimidin-2-yl] -amine derivatives {Microbiocidal N-phenyl-N- [4- (4-pyridyl) -2- pyrimidin-2-yl] -amine derivatives}

Certain N-phenyl-4- (4-pyridyl) -2-pyrimidine amine derivatives are known in the art as pharmacological features, particularly as tumor suppressor anticancer agents, for example in PCT patent applications WO 95/09851 and WO 95/09853. Is disclosed.

Surprisingly, the novel N-phenyl- [4- (4-pyridyl) -pyrimidin-2-yl] -amines have properties that are beneficial for the treatment of plant diseases caused by an individual, and thus have been found in plant protection and related fields. It turns out to be effective.

The present invention is directed to N-phenyl- [4- (4-pyridyl) -pyrimidin-2-yl] -amine derivatives, plants and / or plant parts of N-phenyl- [4 as specified herein below. By applying a-(4-pyridyl) -pyrimidin-2-yl] -amine derivative, a phytopathogenic individual such as a nematode or an insect or in particular a microorganism, preferably fungi, bacteria and viruses, or a combination of two or more of these individuals A method of protecting a plant against attack or infection by, a use of said derivative for protecting a plant from said individual, and a composition comprising said derivative as an active ingredient. The invention also relates to a process for the preparation of these novel N-phenyl- [4- (4-pyridyl) -pyrimidin-2-yl] -amine derivatives.

The novel N-phenyl- [4- (4-pyridyl) -pyrimidin-2-yl] -amine derivatives according to the invention are amine derivatives of formula I or as salts thereof.

(I)

The sum of (m + p) in the formula is 0, 1, 2 or 3;

n and q are each independently 0 or 1 and the sum of (m + p + q) is 1, 2, 3 or 4;

R ₁ is hydrogen, halogen, alkoxy, haloalkyl, haloalkoxy or alkyl;

R ₂ is hydrogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -haloalkyl or C ₁ -C ₆ -alkoxy;

R _2A is hydrogen, C ₁ -C ₆ -alkyl, C ₃ -C ₄ -alkenyl or C ₃ -C ₄ -alkynyl;

R ₃ , R ₄ , R ₅ and R ₆ are each independently of the other hydrogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -haloalkyl, hydroxy-C ₁ -C ₆ -alkyl or C _1- C ₆ -alkoxy-C ₁ -C ₆ -alkyl, or cyclic members CR ₃ R ₄ or CR ₅ R ₆ or CR ₂ R _2A are each independently a carbonyl group (C═O) or a C═S group;

X is C═O, C═S, S═O, or O═S═O;

Y is O, S, C═O, CH ₂ , —N (R ₈ ) —, —ON (R ₈ ) —, —N (R ₈ ) —O— or —NH—;

R ₇ is hydrogen, C ₁ -C ₄ -alkyl, C ₃ -C ₄ -alkenyl, C ₃ -C ₄ -alkynyl, -CH ₂ OR ₈ , CH ₂ SR ₈ , -C (O) R ₈ , -C (O) OR ₈ , SO ₂ R ₈ , SOR ₈ or SR ₈ ; And

R ₈ is C ₁ -C ₈ -alkyl, C ₁ -C ₈ -alkoxyalkyl, C ₁ -C ₈ -haloalkyl or phenyl C ₁ -C ₂ -alkyl wherein said phenyl is halo or C ₁ -C ₄ -alkyl It may be substituted with up to 3 groups selected from.

The general symbols and expressions used above are preferably as defined below:

Halogen is fluorine, boron, iodine or preferably chlorine.

Haloalkyl is preferably C ₁ -C ₆ -alkyl, more preferably lower alkyl, linear or branched and substituted by one or more, for example halo-ethyl, up to 5 halogen atoms, in particular fluorine. One example is trifluoromethyl.

Haloalkoxy is preferably C ₁ -C ₆ -alkoxy, more preferably lower alkoxy, which is linear or branched and substituted by one or more, for example halo-ethyl, up to 5 halogen atoms, in particular fluorine. Especially preferred are trifluoromethoxy and 1,1,2,2-tetrafluoroethoxy.

Alkyl as the structural element of the group itself and of hydroxyalkyl, alkoxy, alkenyl, alkynyl or haloalkoxy is preferably C ₁ -C ₆ -alkyl, more preferably lower alkyl, for example methyl, Straight chains such as ethyl, propyl, butyl, pentyl or hexyl, or branched such as, for example, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl. Lower alkyl is preferably methyl or ethyl. Specific examples of alkenyl and alkynyl include allyl, 2-butenyl, 3-butenyl, propargyl, 2-butynyl and 3-butynyl.

Preferred of the compounds to be used according to the invention are N-linked heterocycles, ie, said sites, attached to position 2 of the pyridine ring.

Is the sum of the index numbers m + p + q is 2, 3 or 4, which represents a variety of 5 to 7-membered ring systems that can be conceived under the given definitions and are common in the heterocyclic industry. More preferably, this site is a 5- and 6-membered ring system (m + p + q is 2 or 3), preferably a 5-membered ring system. Thus, examples of such sites include N-oxazolidin-2-one, N-oxazolidine-2-thione, N- [1,2,3] oxathiazolidine-2-oxide, N- [1, 2,3] oxathiazolidine-2,2-dioxide, N-pyrrolidin-2-one, N-pyrrolidine-2-thione, N-pyrrolidine-2,5-dione, N-thia Zolidin-2-one, N-4-methylene-oxazolidin-2-one, N-piperidine-2,6-dione, N-morpholine-2,3-dione, N-morpholine-2 , 5-dione, N-imidazolidin-2-one, N- [1,2,4] -oxazolidin-5-one, N- [1,2,4] -oxazolidine-3- On, N- [1,2,5] -oxadiazin-6-one, N- [1,2,4] -oxadiazin-3-one, azepan-2-one or [1,3] Oxazin-2-ones are included.

More preferred ring systems for the site located at position 2 of the pyridyl ring are N-oxazolidin-2-one, N-oxazolidine-2-thione, N- [1,2,3] oxathia Compound selected from the group comprising zolidine-2-oxide and N-pyrrolidin-2-one.

The compounds of formula I are for example inorganic acids such as hydrochloric acid, sulfuric acid or phosphoric acid, or for example trifluoroacetic acid, acetic acid, propionic acid, glycolic acid, succinic acid, maleic acid, fumaric acid, hydroxymaleic acid, Fatty acids mono- or di-carboxylic acids such as malic acid, tartaric acid, citric acid, oxalic acid or amino acids such as arginine or lysine, benzoic acid, 2-phenoxy-benzoic acid, 2-acetoxy-benzoic acid, salicylic acid, 4 Aromatic carboxylic acids such as aminosalicylic acid, aromatic-aliphatic carboxylic acids such as madelic acid and cinnamic acid, heteroaromatic carboxylic acids such as nicotinic acid or isnicotinic acid, methane-, ethane-, Or aliphatic sulfonic acids such as 2-hydroxy-ethane-sulfonic acid, or aromatic sulfonic acids, for example suitable organic acid carboxylic acids or sulfones such as benzene-, p-toluene- or naphthalene-2-sulfonic acid The acid addition salts can be formed.

The pyridine-N-oxide of formula I may form an acid addition salt with sulfonic acid such as hydrochloric acid, nitric acid, strong acid such as phosphoric acid, or benzenesulfonic acid.

Formula I according to the invention includes not only all possible isomers, but also mixtures such as racemic mixtures and mixtures of any rotamers.

A close relationship between the compound of formula I in its free form and a salt that can also be used as an intermediate to identify, for example, the purification of a compound of formula I, or a compound of formula I in their salt form In view of the above, the terms (free) compounds described above and below herein are understood to also include corresponding salts for convenience.

Among the compounds of the formula I according to the invention, the following compound groups are preferred. These groups are

R ₁ is chloro, fluoro, trifluoromethyl, trifluoromethoxy or 1,1,2,2-tetrafluoroethoxy, or

R ₁ is chloro, or

R ₂ is hydrogen, methyl, trifluoromethyl or ethyl, or

R ₂ is methyl or trifluoromethyl, or

R ₂ is methyl, or

R _2A is hydrogen or methyl; or

R _2A is hydrogen; or

R ₃ , R ₄ , R ₅ and R ₆ are independently of each other hydrogen, methyl, hydroxymethyl, hydroxyethyl or methoxyethyl, or

One of R ₃ and R ₄ or one of R ₅ and R ₆ is hydrogen or methyl, the other is hydrogen, methyl, hydroxymethyl, hydroxyethyl or methoxyethyl, or

R ₃ and R ₄ are hydrogen, or

R ₅ and R ₆ are independently of each other hydrogen or methyl, or

R ₇ is hydrogen, methyl, ethyl, allyl, propargyl, methoxymethyl, thiomethoxymethyl or ethoxymethyl, or

R ₇ is hydrogen or methoxymethyl, or

X is carbonyl, C = S, or S = O, or

X is carbonyl, or

Y is oxygen, sulfur, -ON (CH ₃ )-, or -N (CH ₃ ) -O-, or

Y is oxygen, or

X is carbonyl, C = S, or S = O, and Y is oxygen,

n is 0, or

m is 0 and p and q are 1, respectively.

Further preferred subgroups are

a) R ₁ is chloro, fluoro, trifluoromethyl, trifluoromethoxy or 1,1,2,2-tetrafluoroethoxy; R ₂ is hydrogen, methyl, trifluoromethyl or ethyl; R _2A is hydrogen or methyl; R ₅ and R ₆ are independently of each other hydrogen, methyl, hydroxymethyl, hydroxyethyl or methoxyethyl; R ₇ is hydrogen, methyl, ethyl, allyl, propargyl, or methoxymethyl; X is carbonyl, C = S, or S═O, Y is oxygen, sulfur, —ON (CH ₃ ) —, or —N (CH ₃ ) —O—; m and n are 0 and p and q are each 1; or

b) R ₁ is chloro; R ₂ is methyl or trifluoromethyl; R _2A is hydrogen or methyl; One of R ₅ and R ₆ is hydrogen or methyl and the other is hydrogen, methyl, hydroxymethyl, hydroxyethyl or methoxyethyl; R ₇ is hydrogen or methoxymethyl; X is carbonyl and Y is oxygen; m and n are 0 and p and q are each 1; or

c) R ₁ is chloro; R ₂ is methyl; R _2A is hydrogen; R ₅ and R ₆ are independently of each other hydrogen or methyl; R ₇ is hydrogen or methoxymethyl; X is carbonyl; Y is oxygen; m and n are 0 and p and q are 1, respectively.

Preferred individual compounds of formula I are the following compounds:

3- {4- [2- (3-Chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2yl} -oxazolidin-2-one,

N- {4- [2- (3-Chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -pyrrolidin-2-one,

(3-Chloro-phenyl)-{4- [2- (2-oxo- [1 2,3] oxathiazolidin-3-yl) -pyridin-4-yl] -pyrimidin-2-yl}- Amine,

3- {4- [2- (3-fluoro-phenylamino) -pyrimidin-4yl] -pyridin-2-yl} -4-methyl-oxazolidin-2-one,

3- {4- [2- (3-trifluoromethyl-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -4-methyl-oxazolidin-2-one,

(3-Chloro-phenyl)-{4- [2- (4-methyl-2-oxo- [1 2,3] oxathiazolidin-3-yl) -pyridin-4-yl] -pyrimidine-2 -Yl} -amine,

1- {4- [2- (3-Chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -5-methyl-pyrrolidin-2-one,

3- {4- [2- (3-chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -4-ethyl-oxazolidin-2-one,

3- {4- [2- (3-chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -4-n-propyl-oxazolidin-2-one,

3- {4- [2- (3-chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -4-i-propyl-oxazolidin-2-one,

3- {4- [2- (3-Chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -5-methyl-oxazolidin-2-one,

3- {4- [2- (3-Chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -4-methyl-oxazolidin-2-one,

3- {4- [2- (3-chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -4-methyl-oxazolidine-2-thione,

(S) -3- {4- [2- (3-chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -4-methyl-oxazolidin-2-one,

3- {4- [2- (3-chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -4-trifluoromethyl-oxazolidin-2-one,

(R) -3- {4- [2- (3-chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -4-methyl-oxazolidin-2-one,

3- {4- [2- (3-Chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -4-trifluoromethyl- [1,3] oxazinan-2-one ,

3- {4- [2- (3-chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -4-methyl- [1,3] oxazinan-2-one,

1- {4- [2- (3-Chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -5-trifluoromethyl-pyrrolidin-2-one, and

3- (4- {2-[(3-chloro-phenyl) -methoxymethyl-amino] -pyrimidin-4-yl} -pyridin-2-yl) -4-methyl-oxazolidin-2-one .

The compounds according to the invention can be prepared according to the methods per se known in the art (although this means that each of the above preparation methods is also novel if a new compound is prepared). The preparation of the compounds of formula I can be summarized as follows:

A) a compound of formula (II) having a meaning given for the compound of formula I, wherein U is a leaving group, in particular halogen, for example fluoro, chloro, bromo or iodo Salt)

(II)

R ₂ to R ₆ , R _2A , X, Y, m, p and q are cyclic amine ring systems (or salts thereof) of formula III having the meanings given for compounds of formula I

(III)

Reacting with a base and a metal catalyst such as a palladium (II) or palladium (0) complex or in the presence of a base, such as sodium hydride, potassium carbonate, potassium tert-butoxide, or

B) R ₁ to R ₇ , R _2A , X, Y, n, m, p and q have the meaning given for compounds of formula I and U 'is a leaving group, in particular halo such as chloro, bromo or iodo Compounds of formula IV that are sulfonyloxy, such as mesyloxy, trifluoromethanesulfonyloxy, tosyloxy or benzenesulfonyloxy

(IV)

Optionally cyclizing by heating in the presence of a base such as pyridine, triethylamine, sodium carbonate, or the like, or

C) q is 1 and R ₁ , R ₂ , R _2A , R ₅ , R ₆ , R ₇ , Y, n and p represent compounds of formula V having the meanings given for compounds of formula I

(V)

Reacted with phosgene, di- or triphosgen, carbonyldiimidazole, thiophosgene, thiocarbonyldiimidazole or thionylchloride, where X is C = O, C = S or S = O, q is 1, Compounds of subformula Ia wherein R ₁ , R ₂ , R _2A , R ₅ , R ₆ , R ₇ , Y, n and p have the meaning given to the compound of formula I

(Ia)

To obtain, or

D) R ₁ to R ₇ , R _2A , Y, n, m, p and q are compounds of corrosion Ib having the meanings given for the compound of formula I

(Ib)

Oxidizing with an oxidizing amount of an oxidizing agent such as NaIO ₄ / RuCl ₃ , NaOCl / RuO ₂ or KMnO ₄ to form a compound of formula I wherein X is O = S═O, or

E) a compound of Formula VI wherein R ₁ to R ₇ , R _2A , Y, n, m, p and q have the meanings given for the compound of Formula I

. (VI)

Reacting with an oxidizing amount of an oxidizing agent such as iodine to form a compound of formula I wherein X is S═O.

Reaction Forms A to E and additional methods that can be applied as such or as a similar process to the synthesis of compounds of Formula I are described, for example, in Organic Letters 2 (8), 1101-1104 (2000); Organic Letters 3 (16), 2539-2541 (2001); Organic Letters 2 (5), 625-627 (2000); Tetrahedron Letters 40 (11), 2035-2038 (1999); Heterocycles 48 (3), 481-489 (1998); Journal of Organic Chemistry 55 (13), 4156-4162 (1990); Journal of Organic Chemistry 58 (3), 696-699 (1993); Journal of Organic Chemistry 50 (l), 1-4 (1985); British Patent Application GB 2267287 A (1993); European Patent Application EP-A-497695 (1992); Organic Magnetic Resonance 12 (8), 481-489 (1979); Journal of the Chemical Society, Perkin Trans. 2, 1207-1210 (1978); Japanese Patent Application JP 54024869 (1979); Yakugaku Zasshi 98 (6), 817-821 (1978); Heterocycles 7 (2), 919-925 (1977); Chemical Abstracts 77: 139931; Zhurnal Organicheskoi Khimii 6 (6), 1305-1308 (1970). Suitable palladium catalysts for the CN bond reaction (Buchwald-Hartwig amination) of the compound of Formula II with the cyclic amine ring system of Formula III are generally palladium (II) or palladium (0) It is a complex. These catalysts can be prepared in separate steps, such as, for example, dichloro [1,1'-bis (diphenylphosphino) ferrocene] palladium or PdCl ₂ (BINAP). The palladium catalyst also contains palladium (II), such as palladium (II) dichloride, palladium (II) acetate, bis (dibenzylideneacetone) palladium (0), tris (dibenzylideneacetone) dipalladium, and corresponding ligands. Or in situ from a palladium (0) compound.

Examples of suitable ligands include tris (tert-butyl) phosphine, tricyclohexylphosphine (PCy3), 2,2 '-(diphenylphosphino) -bisnaphthalene (BINAP), 1,1'-bis (diphenyl Phosphino) ferrocene (dppf), 1,1'-bis (di-tert-butylphosphino) ferrocene, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane , 1,4-bis (diphenylphosphino) butane, bis (2- (diphenylphosphino) phenyl) ether (DPE-phos), 4,5-bis (diphenylphosphino) -9,9-dimethyl Dimethylxanthanene (Xantphos), 2- (di-tert-butylphosphino) biphenyl, 2- (dicyclohexylphosphino) biphenyl, 2-dicyclohexylphosphino-2 '-(N, N '-Dimethylamino) biphenyl, 2-di-tert-butylphosphino-2'-(N, N'-dimethylamino) biphenyl is included but is not limited thereto.

Examples of bases include, for example, sodium tert-butoxide, potassium tert-butoxide, sodium amide, lithium diisopropyl amide (LDA), lithium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, sodium methyl Bases such as latex, sodium phenolate, CS ₂ CO ₃ , K ₃ PO ₄ .

The compounds of the formulas II, V and VI can be prepared according to the preparation methods described in WO 95/09853 or in a manner analogous to the methods described above.

Compounds of Formula III are known or are known as Organic Letters 2 (5), 625-627 (2000); It may be prepared by a method similar to the patent application EP-A-350002 (1990) or the synthetic method described in the above document.

The compound of formula IV is novel and R ₁ , R ₇ and n represent compounds of formula VII having the meanings given for compounds of formula I.

(VII)

R ₂ to R ₆ , R _2A , U ', X, Y, m, p and q have the meaning given for compounds of formula IV, where U ″ forms a leaving group or anhydride such as chloro in particular It can be prepared by reacting with a compound of formula VIII which is oxygen.

Methods for the preparation of compounds of formula VII are described in PCT application WO 95/09851.

The compound of formula II wherein R ₇ is hydrogen is preferably L is a leaving group, preferably alkoxy such as lower alkoxy, esterified OH (particularly tosyloxy), or di- (lower alkylamino), and U is Is a leaving group (preferably halo, such as chloro, bromo or iodo), and n is 0 or 1, wherein the compound of formula IX (or-if n is 0-a salt thereof)

(IX)

A guanido compound (or salt thereof) of Formula X, wherein R ₁ is defined for the compound of Formula I

(X)

It can be obtained by reacting.

The reaction is preferably carried out under suitable conditions as in the process disclosed in PCT application WO 95/09583, i.e. at room temperature (about + 20 ° C) to + 150 ° C, for example at reflux with a suitable solvent or suspending agent, for example isopropanol Or in a suitable alcohol such as 2-butanol.

The compound of formula II wherein R ₇ is —CH ₂ OR ₈ , —C (O) R ₈ or —C (O) OR ₈ , preferably comprises a compound of formula II wherein R ₇ is hydrogen with one of the Can be obtained by reaction: Hal-CH ₂ OR ₈ , Hal-C (O) R ₈ , Hal-C (O) OR ₈ rasp., O (C (O) R ₈ ) ₂ , wherein Hal is chlorine, Halogen, such as boron or iodine.

The compound of formula IX is known, for example n is 0 or 1 and U is a leaving group, preferably a compound of formula XI as defined for the compound of formula IX

(XI)

(i) under Claisen or pseudo-condensation reaction conditions (induced by free hydroxy instead of leaving group L in the compound of formula IX; this free hydroxy group is for example alkylalcohol ("alkoxy-H To alkoxy as L, such as lower alkoxy, by ether formation reaction with ") or to OH (especially tosyloxy) esterified by reaction with an acid or acid ester derivative, for example an acid chloride; or May be converted to a leaving group such as to alkoxy L, depending on the conditions), or (ii) analogously to the procedure described in European patent application EP-A-0233461, which is preferably incorporated herein by reference. , Reaction with N, N-di- (lower alkyl) -formamide di-lower alkyl acetal, preferably N, N-di- (methyl) formamide di-methylacetal, for example at room temperature Ratio of mixture Temperature, preferably, each of N, N- di-under reflux conditions between the (lower alkyl) formamide di-lower alkyl, by reaction of the acetal, and may be prepared according to methods known in the art.

Intermediates of the above formula (XI) are, for example, metalized methyl derivatives of the formula (XII) wherein the metal preferably represents Mg-Hal (Hal = halogen) or Li

CH ₃ -metal (XII)

U and n have the meaning given for the compound of formula IX above, W is a leaving group, preferably N-lower alkyl-N-lower alkoxy-amino or halogen 4-pyridyl-carboxylic acid of formula (XIII) With derivatives

(XIII)

It can be obtained by reacting under standard conditions for the alkylation reaction.

In addition, intermediates of formula XI where n is 0 are as defined for compounds of formula IX where U is a leaving group, preferably metallized of formula XIV wherein Mg-Hal (Hal = halogen) or Li Pyridine derivatives

(XIV)

Z is halo or forms amide, alkoxyamide, anhydride and the like with the rest of the molecule; Or an acetyl equivalent of formula XV wherein Z is hydrogen (compound XV means acetaldehyde)

(XV)

By reaction, the alcohol obtained after the reaction can be obtained by oxidizing with a selective oxidizing agent, for example to the ketone intermediate of formula XI in the presence of oxalylchloride and dimethyl sulfoxide.

The starting material of Formula X is aniline derivatives of Formula XVI wherein R ₁ is defined for the compounds of Formula I.

(XVI)

In a suitable solvent, for example an alcohol such as lower alkanol, for example, in the presence of (i) the same molar amount of salt-forming acid, for example nitric acid, or (ii) hydrochloric acid, for example clear, for example In the presence of an excess of 60% mineral acid (when the ammonium salt of the desired salt-forming acid is added, the reaction is completed), it can be obtained by reacting at a temperature between room temperature and + 150 ° C., for example under reflux. (Preferably an acid addition salt).

Compounds of formulas XIII, XIV and XVI can be prepared according to methods known in the art.

Many such starting materials and intermediates may also be synthesized by the methods described in WO 95/09853 or similar methods.

In all intermediates, functional groups that should not participate in the desired reaction are protected and deprotected at appropriate stages to avoid side reactions-suitable protecting groups and methods for introducing and removing them are disclosed, for example, in WO 95/09853.

The present invention also relates to novel starting materials and / or intermediates and methods for their preparation. The starting materials used and the reaction conditions chosen are particularly preferably or particularly preferably used so that such compounds disclosed herein are obtained. Particularly preferred of the above process conditions are those described in the examples below, or similar conditions.

The invention also relates to compositions comprising the compounds of the above formula I, or their salts, as active ingredients, especially in plant-protective compositions, and their use in the agricultural or related fields.

The active compounds of formula I are usually used in the form of compositions and may be added simultaneously or sequentially with additional active compounds to the surface or plant to be treated. These additional active compounds may be one of fertilizers, trace element-feeders or other compositions that affect plant growth. In this sense, optional herbicides such as insecticides, fungicides, bactericides, nematicides or fungicides, or mixtures of these various compositions, if appropriate additionally excipients, surfactants Or other administration-promoting additives (collectively referred to herein as carrier materials) that are customary in formulation technology.

Suitable excipients and additives may be in solid or liquid form and are suitable materials for the formulation technique, for example natural or renewable minerals, solvents, dispersants, wetting agents, adhesives, thickening agents, binders. Or fertilizer.

A preferred method of applying a compound of formula I, or an agrochemical composition comprising at least one of these compounds, is to administer to the leaves (leaf spray). The frequency and rate of administration depend on the risk of infection by the pathogen. However, compounds of formula I can also penetrate the plant through the roots through the soil (systemic action). The locus of the plant may be impregnated with a liquid formulation or the substance may be introduced into the soil in solid form, for example in the form of granules, for administration (soil spraying). In rice crops, such granules can be applied to paddy fields in measured quantities. However, to treat seeds, the compounds of formula I can also be applied (coated) to the seeds by saturating the grains or tubers with liquid formulations of the active ingredient or by coating them with solid phase formulations.

Beneficial application rates are usually 5 g to 2 kg active ingredient (a.i.) / Ha (ha), preferably 10 g to 1 kg a.i./ha, in particular 20 g to 600 g a.i./ha. When the compound is used as a seed dressing agent, a dosage of 10 mg to 1 g active ingredient / kg seed may advantageously be employed. The agrochemical composition usually comprises 0.1 to 99% by weight of the compound of formula I, preferably 0.1 to 95% by weight, 99.9 to 1% by weight of solid or liquid adjuvant, preferably 99.8 to 5% by weight, and 0 to 0% of surfactant. 25% by weight, preferably 0.1 to 25% by weight. If a commercial product is desired to be formulated as a concentrate, end users usually use dilute formulations.

The composition may also contain auxiliary, such as fertilizers and other active ingredients, to achieve a particular desired biological effect.

The compound of formula I may be used prophylactically and / or therapeutically in agriculture and related arts as the active ingredient for controlling plant pests. The active ingredient of the formula I according to the present invention has the advantage of showing good activity even at low concentration, good plant tolerance (tolerance), and environmentally friendly. The compounds have very beneficial, especially systemic properties, and can be used to protect many cultivars. By using the active ingredients of formula I in plants or parts of plants (fruits, flowers, leaves, stems, tubers, roots) of various crops, it is possible to control or eliminate emerging pests, so that parts of plants that grow on seedlings For example, it may also be protected from plant pathogenic microorganisms.

Common sense compound I can additionally be used as a dressing to treat seeds (fruits, tubers, corn) and plant cuttings to protect against fungal infections and plant pathogenic microorganisms present in the soil.

Compound I is effective, for example, on related phytopathogenic fungi of the following classes: Fungi imperfecti (e.g., Botrytis , Pyricularia , Helminthosporium , Fusarium , Septoria , Cercospora and Alternaria ) and Basidiomycetes (e.g. Rhizoctonia , Hemileia , Puccinia ); It is effective against Ascomycetes (e.g., Venturia and Erysiphe , Poclosphaera , Monilinia , Uncinula ) and Oomycetes (e.g. Phytophthora , Pythium , Plasmopara ).

In the context of the present invention, target crops for plant-protective use include the following cultivar: cereals (wheat, barley, rye, oats, rice, corn, sugarcane) Related species); Beets (sugar beet and fodder beet); Pome, stone and berry fruits (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberry and raspberry and Blackberry); Leguminous plants (beans, lentils, peas, soybeans); Oil crops (flat, mustard, poppy, olives, sunflowers, coconuts, castor oil plants, cocoa beans, peanuts); Cucumber plants (squash, cucumber, melon); Citrus fruit (orange, lemon, grapefruit, mandarin); Vegetables (spinach, lettuce, asparagus, cabbage varieties, carrots, onions, tomatoes, potatoes, paprika; laurel (avocado, cinnamomum, camphor) or decorative plants, Plants such as tobacco, nuts, coffee, eggplants, sugar cane, tea, peppers, vines, hops, bananas and natural rubber plants.

A further field of application of the active ingredient according to the invention is the field of storage and the protection of materials in which the storage material is protected against decay and mildew.

Compound I is used in unmodified form or preferably with excipients customary in the formulation art. For this purpose, the compounds are conveniently processed by known methods, for example emulsifiable concentrates, coatable pastes, direct sprayable or dilutable solutions, dilute emulsions, wettable powders. , Soluble powders, dusts or granules, for example granules by encapsulation in a polymeric material. For the form of the medium, application methods such as spraying, atomizing, dusting, scattering, coating or pouring are selected according to the intended use and the prevailing environment. do.

Suitable materials and additives may be solid or liquid and may be useful in the formulation art, for example, natural or renewable mineral materials, dissolving aids, dispersions, wetting agents, tackifiers, thickeners. Thickener or binding agent.

The compounds of the general formula I can be mixed with further active ingredients, such as fertilizers, ingredients which provide micronutrients or other active ingredients used in plant protection, in particular further fungicides. By doing so, in some cases a synergistic increase in biological effect may occur.

Preferred active ingredients which are beneficial as additives to the composition comprising the active ingredient of formula I are as follows:

Azaconazole, BAY 14120, Vitertanol, Bromuconazole, Ciproconazole, Diphenoconazole, Diniconazole, Epoxyconazole, Penbuconazole, Fluquinconazole, Flusilazole, Flutripol, Hexacona Sol, imazalyl, imibenconazole, ifconazole, metconazole, michaelrobutanyl, pefurazoate, fenconazole, pyriphenox, prochloraz, propiconazole, simeconazole, Azoles such as tebuconazole, tetraconazole, triadimefon, triadimenol, triflumiazole, or triticazole; Pyrimidinyl carbinols such as ancymidol, fenarimol or noarimol; 2-amino-pyrimidine, such as buprimate, dimethirimol or etirimole; Morpholines, such as dodemorph, fenpropidine, fenpropimod, spiroxamine or tridemorph; Anilinopyrimidines such as ciprodinyl, pyrimethanyl or mepanipyrim; Pyrroles such as fenpiclonyl or fludioxonil; Phenylamides such as benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, offlace or oxadixyl; Benzimidazoles such as benomyl, carbendazim, devacarb, fuberidazole or thiabendazole; Dicarboximide such as clozolinate, diclozoline, iprodione, microzoline, procmidone or vinclozoline; Carboxamides such as carboxycin, fenfuram, flutolanyl, mepronyl, oxycarboxycin or tifluzamide; Guanidines such as guazin, dodine or imineoctadine; Strobilurine, such as azoxystrobin, cresoximemethyl, metominostrobin, SSF-129, triplexoxystrobin, peacockcistrobin, BAS 500F (proposed designation pyraccloscrobin), BAS 520 ); Dithiocarbamates such as ferbam, mancozeb, maneb, metiram, propineb, thiram, geneb or ziram; N-halomethylthiotetrahydrophthalimide, such as captapol, captan, diclofluanide, fluoromide, polpet or tolifluanide; Copper-compounds such as Bordeaux mixture, copper hydroxide, kappa oxychloride, kappa sulfate, cuprus oxide, mankapa or auxin-kappa; Nitrophenol derivatives such as dinocap or nitrotal-isopropyl; Organic phosphorus derivatives such as edifeneforce, ifprobenfos, isoprothiolane, phosphodifen, pyrazophos or toclofos-methyl; And acibenzola-S-methyl, aniazine, ventiavalicarb, blastidine-S, chinomethionat, chloroneb, chlorothalonil, cyflufenamide, cymosanyl, diclones, Diclomezin, dichloran, dietofencarb, dimethomorph, SYP-LI90 (proposed name: flumorph), dithianon, etaboksam, ethriazole, pamoksadon, phenamidone, phenoxa Neil, Pentin, Perimzone, Fluazinam, Flusulfamid, Phenhexamide, Pocetyl-Aluminum, Himexazole, Iprovalicarb, IKF-916 (Cyazopamide), Kasugamycin, Metasulfocarb , Methrafenone, nicobiphene, penicuron, phthalide, polyoxin, probenazole, propamocarb, pyroquilon, quinoxyphene, quintogen, sulfur, thiaside, tricyclazole, tripolin, valinda And various other compounds such as mycin, oxamid (RH7281).

A preferred method of applying the active ingredient of Formula I, or an agrochemical composition comprising at least one of these active ingredients, is foliar spraying. The frequency and amount of application depends on the severity of the attack by the pathogen. However, the active ingredient of formula I also reaches the plant through the root system via the soil by saturating the locus of the plant in liquid formulation or by binding the substance to the soil in solid form, for example in the form of granules. (Systemic action) (soil application). In rice cultivation, such granules can be applied to water paddy. However, the compounds of formula I can also be applied to seed grains for the treatment of seed material (coating), in which case the grains or tubers are saturated with the liquid formulation of the active ingredient or coated as a solid formulation.

The compositions of the present invention can be prepared by known methods, for example by intimate mixing and / or grinding of the active ingredient with extenders such as solvents, solid carriers and optionally surfactants.

Preferred application rates are generally 1 g to 2 kg active ingredient (AS) / ha (ha), preferably 10 g to 1 kg AS / ha, in particular 20 g to 600 g AS / ha. When used as a seed dressing, it is advantageous to use a dosage of 10 mg to 1 g active substance / kg seed grain.

While concentrated compositions are preferred for commercial use, end users usually use diluted compositions.

The formulations can be prepared, for example, similarly to the formulations described in WO 97/33890.

The following examples are intended to illustrate the invention and do not limit the scope of the invention.

Synthetic Example 1 3- {4- [2- (3-Chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2yl} -oxazolidin-2-one

Phosgene in toluene (1.9 ml of 20% commercial solution, 3.5 mmol) was dissolved in 2- {4- [2- (3-chloro-phenylamino) -pyrimidin-yl] -pyridinyl amino} ethanol in absolute THF (20 ml) 0.88 g, 2.6 mmol) and triethylamine (1.7 ml, 11.7 mmol) were added at 50 ° C. within 5 minutes. The resulting suspension was stirred for 1 hour at room temperature and then partitioned between ethyl acetate and water. The organic phase was separated, dried over magnesium sulphate, filtered and evaporated under reduced pressure. The residue was purified by silica gel chromatography to give m.p. The title compound was obtained which is 162-163 ° C.

Synthetic Example 2 3- {4- [2- (3-Chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2yl} -oxazolidine-2-thione

2- {4- [2- (3-chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2-ylamino} -ethanol (0.67 g, 2.Ommol) and thio in absolute THF (20 ml) A mixture of carbonyldiimidazole (0.38 g, 2.1 mmol) was stirred at rt for 1 h. The reaction mixture was partitioned between ethyl acetate and water. The organic phase was separated, dried over magnesium sulphate, filtered and evaporated under reduced pressure. The residue was purified by silica gel chromatography to give m.p. The title compound was obtained at 213-214 ° C.

Synthetic Example 3: (3-Chloro-phenyl)-{4- [2- (2-oxo- [1,2,3] oxathiazolidin-3-yl) -pyridin-4-yl] -pyrimidine -2-yl} -amine

Sulfonylclide solution (0.63 g, 5.3 mmol) in THF (20 ml) was added to 2- {4- [2- (3-chloro-phenylamino) -pyrimidin-4-yl] -pyridine- in absolute THF (20 ml). To a solution of 2-ylamino} -ethanol (1.50 g, 4.4 mmol) and triethylamine (3.O ml, 22 mmol) was added at + 5 ° C. within 5 minutes. The resulting suspension was stirred at room temperature for 4 hours and then partitioned between ethyl acetate and water. The organic phase was separated, dried over magnesium sulphate, filtered and evaporated under reduced pressure. The residue was purified by silica gel chromatography to give m.p. The title compound was obtained at 202-203 ° C.

Synthetic Example 4 1- {4- [2- (3-Chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -pyrrolidin-2-one

In a solution of (3-chloro-phenyl)-[4- (2-chloro-pyridin-4-yl) -pyrimidin-2-yl] -amine (4.8 g, 0.015 mol) in pyrrolidone (20 ml) Divided into fractions, sodium hydride (1.93 g, 0.06 mmol, 75% dispersed in oil) was added. The reaction temperature was slowly raised to +150 ° C. After 30 minutes, the heating bath was removed and the mixture was poured onto crushed ice. The mixture was partitioned between ethyl acetate and water. The organic phase was separated, dried over magnesium sulphate, filtered and evaporated under reduced pressure. The residue was purified by silica gel chromatography, recrystallized from ethyl acetate and m.p. The title compound was obtained which is 165-166 ° C.

Synthetic Example 5: 3- (4- {2-[(3-Chloro-phenyl) -methoxymethyl-aminol-pyrimidin-4-yl} -pyridin-2-yl) -4-methyl-oxazoli Din-2-one

Potassium t-butoxide (0.235 g, 2.1 mmol) was added 3- {4- [2- (3-chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -4-methyl at room temperature. Add to a solution of oxazolidin-2-one (0.5 g, 1.3 mmol). The mixture was stirred for 10 minutes and then chloromethylmethylether (0.17 g, 2.1 mmol) in THF (3 ml) was added. The mixture was stirred at this temperature for a further 5 hours. Diluted with ethyl acetate, washed with brine, dried over magnesium sulfate, filtered and the solvent was evaporated to afford the title compound in the form of a slightly colored oil; ¹ H-NMR (DMSO): 8.70 (s, 1 H); 8.51 (d, 1 H); 8.48 (d, 1 H); 7.68 (d, 1 H); 7.47-7.23 (m, 5 H); 5.39 (s, 2 H); 4.87-4.74 (m, 1 H); 4.50 (dd, 1 H); 4.08 (dd, 1 H); 3.25 (s, 3 H); 1.33 (d, 3 H).

Synthetic Example 6 1- {4- [2- (3-Chloro-phenylamino) -pyrimidin-4-yll-pyridin-2-yl} -5-methyl-pyrrolidin-2-one

(3-chloro-phenyl)-[4- (2-chloro-pyridin-4-yl) -pyrimidin-2-yl] -amine (0.95 g), NaOtBu (0.29 g), in Schlenk tubes, dppf (0.1 g), Pd (OAC) ₂ (0.01 g) and 4-methylpyrrolidin-2-one (0.2 g) were added: vacuum / argon was added three consecutive times. Thereafter, 100 ml of degassed dioxane was added and the solution was heated to 120 ° C. (external temperature) for 8 hours. The solvent was removed in vacuo and the crude product was purified via column chromatography (eluent; EE / MeOH = 9/1) to afford the title compound as mp 162-164 ° C.

Synthetic Example 7: 3- {4- [2- (3-Chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -4-methyl-oxazolidin-2-one

A solution of Xantphos (0.018 g) and Pd ₂ (dba) ₃ (0.014 g) in toluene (2 ml) was stirred under argon at room temperature for 20 minutes. Next, (3-chloro-phenyl)-[4- (2-chloro-pyridin-4-yl) -pyrimidin-2-yl] -amine (0.20 g), (R) methyl-oxazolidine-2 -One (0.127 g), NaOtBu (0.085 g) and toluene ((2 ml) were added The reaction mixture was refluxed at 120 ° C. The mixture was then cooled to room temperature and diluted with ethyl acetate The organic layer was dried over Na ₂ SO ₄ and concentrated in vacuo The residue was purified by silica gel chromatography at mp 177-178 ° C. and [α] _D = −72.0 ° (20 ° C., c = 1) to give the title compound.

Similar to the above examples, the compounds of the following table can also be obtained.

Table 1

R ₂ -R ₆ , R _2A , X, Y, m, p and q are the compounds of formula 1.1 corresponding to one row of Table A.

(I.1)

Table 2

R ₂ -R ₆ , R _2A , X, Y, m, p and q are the compounds of formula I.2 corresponding to one row of Table A.

(I.2)

Table 3

R ₂ -R ₆ , R _2A , X, Y, m, p and q are compounds of formula I.3 corresponding to one row of Table A.

(I.3)

Table 4

R ₂ -R ₆ , R _2A , X, Y, m, p and q are compounds of formula I.4 corresponding to one row of Table A.

(I.4)

Table 5

R ₂ -R ₆ , R _2A , X, Y, m, p and q are compounds of formula I.5 corresponding to one row of Table A.

(I.5)

Table 6

R ₂ -R ₆ , R _2A , X, Y, m, p and q are compounds of general formula I.6 corresponding to one row of Table A.

(I.6)

Table 7

R ₂ -R ₆ , R _2A , X, Y, m, p and q are compounds of general formula I.7 corresponding to one row of Table A.

(I.7)

Table 8

R ₂ -R ₆ , R _2A , X, Y, m, p and q are compounds of formula I.8 corresponding to one row of Table A.

(I.8)

Table 9

R ₂ -R ₆ , R _2A , X, Y, m, p and q are compounds of formula I.9 corresponding to one row of Table A.

(I.9)

Table 10

R ₂ -R ₆ , R _2A , X, Y, m, p and q are compounds of formula I.10 corresponding to one row of Table A.

(I.10)

Table 11

R ₂ -R ₆ , R _2A , X, Y, m, p and q are compounds of general formula I.11 corresponding to one row of Table A.

(I.11)

Table 12

R ₂ -R ₆ , R _2A , X, Y, m, p and q are compounds of general formula I.12 corresponding to one row of Table A.

(I.12)

Table 13

R ₂ -R ₆ , R _2A , X, Y, m, p and q are compounds of general formula I.13 corresponding to one row of Table A.

(I.13)

Table 14

R ₂ -R ₆ , R _2A , X, Y, m, p and q are compounds of general formula I.14 corresponding to one row of Table A.

(I.14)

Table 15

R ₂ -R ₆ , R _2A , X, Y, m, p and q are compounds of general formula I.15 corresponding to one row of Table A.

(I.15)

Table 16

R ₂ -R ₆ , R _2A , X, Y, m, p and q are compounds of general formula I.16 corresponding to one row of Table A.

(I.16)

Table 17

R ₂ -R ₆ , R _2A , X, Y, m, p and q are compounds of general formula I.17 corresponding to one row of Table A.

(I.17)

Table 18

R ₂ -R ₆ , R _2A , X, Y, m, p and q are compounds of formula I.18 corresponding to one row of Table A.

(I.18)

Table 19

R ₂ -R ₆ , R _2A , X, Y, m, p and q are compounds of general formula I.19 corresponding to one row of Table A.

(I.19)

Table 20

R ₂ -R ₆ , R _2A , X, Y, m, p and q are compounds of general formula I.20 corresponding to one row of Table A.

(I.20)

Table A:

Physico-chemical data were obtained for the following exemplary compounds and indicated to illustrate the practice of the present invention, including the synthetic methods outlined. The numerical values given are not to be construed as limiting the invention.

Table B:

Pure Enantiomer

** NMR (Reference: Example 5, Experimental Part)

The following provides an example of a plant protection test system that can illustrate the efficacy of a compound of Formula I (“active ingredient” or “test compound”).

Example B-1 Wheat Mill Puccinia graminis Effect on (brownrust of wheat)

a) residual protection activity

Was treated with the compound (0.02% active substance) 1 primary wheat plant cultivars (. Cv) The formulated test the arena (Arina) in a spray chamber. Two days after application, wheat plants were inoculated by spraying a spore suspension (1 × 10 ⁵ ureidospore / ml) on the test plants. After 1 day incubation at + 20 ° C. and 95% relative humidity (rh), the plants were stored in a greenhouse for 9 days at + 20 ° C. and 60% relative humidity. Disease occurrence was examined 10 days after inoculation.

The compounds in Tables 1-20 showed good activity for this test.

At the indicated concentrations, compounds 1.002, 1.002 *, 1.024, 1.080 and 7.002 showed over 70% fungal infection control in this test.

b) systemic action

An aqueous spray solution (0.002% active material, based on soil volume) prepared from the formulated test compound was poured into a pot with 5 day old wheat plants. Care was taken not to close the spray liquid on the ground portion of the plant. After 4 days, the plants were inoculated with a fungus spore suspension (1 × 10 ⁵ ureidospoa / ml). After incubation for 1 day (humidity 95-100% rh and temperature + 20 ° C), the plants were placed in a greenhouse at + 20 ° C. Ten days after infection, disease development was examined.

The compounds in Tables 1-20 showed good activity for this test.

Example B-2: Tomato Top Phytophthora infestans Effect on (tomato blight)

a) residual protection activity

Three week tomato plant varieties (cv.) Roter Gnom were treated with test compounds formulated in a spray chamber (0.02% active material). Two days after application, the plants were inoculated by spraying a sporeangia suspension (2 × 10 ⁴ spore sacs / ml) onto the test plants. After incubation for 4 days at + 18 ° C. and 95% relative humidity (rh) in the growth chamber, disease development was examined.

The compounds in Tables 1-20 showed good activity for this test.

At the indicated concentrations, compounds 1.002 *, 1.079 and 7.002 showed over 70% fungal infection control in this test.

b) systemic action

An aqueous suspension (0.002% active material, based on soil volume) prepared from the formulated test compound was poured into a pot with 3 day old plants. Care was taken not to close the spray solution on the ground portion of the plant. After 4 days, the plants were inoculated with a fungus sporangia suspension (2 × 10 ⁴ spore sacs / ml). After incubation for 4 days at + 18 ° C. and 95% relative humidity (rh) in the growth chamber, disease development was examined.

The compounds in Tables 1-20 showed good activity for this test.

At the indicated concentrations, compounds 1.002 *, 1.079 and 7.002 showed over 70% fungal infection control in this test.

Example B-3: Effect against Phytophthora infestans / Potato (Potato plague)

Five main potato plant varieties (cv.) Bintje were treated with test compound (0.02% active material) formulated in a spray chamber. Two days after application, the plants were inoculated by spraying a sporangia suspension (1.4 × 10 ⁵ spore sacs / ml) onto the test plants. After incubation for 4 days at + 18 ° C. and 95% relative humidity (rh) in the growth chamber, disease development was examined.

The compounds in Tables 1-20 showed good activity for this test.

Example B-4: Grape Vine Plasmopara viticola Effect on (downy mildew)

Was treated with 5 major grape plant (seedling) cultivar (cv.) Obtain a test compound (0.02% active substance) formulated the tedel (Gutedel) in a spray chamber. One day after application, grape plants were inoculated by spraying a sporangia suspension (4 × 10 ⁴ spore sac / ml) on the lower leaf side of the test plant. After incubation for 6 days in a greenhouse at + 22 ° C. and 95% relative humidity (rh), disease development was examined.

The compounds in Tables 1-20 showed good activity for this test.

Example B-5: Apple Top Venturia inaegualis Residual Protective Effects against Apples (Scab)

Four main apple plant varieties (cv.) McIntosh were treated with test compounds formulated in a spray chamber (0.02% active material). One day after application, apple plants were inoculated by spraying a spore suspension (4 × 10 ⁵ conidia / ml) on the test plants. After 4 days of incubation at + 20 ° C. and 95% relative humidity, the plants were transferred to standard greenhouse conditions at + 20 ° C. and 60% relative humidity and stayed for 2 days. After another four days of incubation at + 20 ° C. and 95% relative humidity, the disease development was examined.

The compounds in Tables 1-20 showed good activity for this test.

At the indicated concentrations, compounds 1.002, 7.002 and 6.002 showed over 70% fungal infection control in this test.

Example B-6: Barley Top Erysiphe graminis Effects on (powdery mildew)

a) residual protection activity

And then treated with barley plant varieties of height about 8cm (cv.) The test compound (0.02% active substance) formulated the Regina (Regina) at the spraying chamber, and applying 2, were inoculated with conidia of the fungus (fungus) ( dusted). The infected plants were placed in a greenhouse at +18 ° C. Six days after infection, fungal attack was examined.

The compounds in Tables 1-20 showed good activity for this test.

At the indicated concentrations, compounds 1.002, 1.003, 1.024, 14.002, 15.002 and 7.002 showed over 70% fungal infection control in this test.

b) systemic action

An aqueous spray (0.002% active material, based on soil volume) prepared from the formulated test compound was poured into a pot with 5 day old barley plants. Care was taken not to close the spray solution on the ground portion of the plant. After 4 days, the plants were inoculated with conidia of the fungus. The infected plants were placed in a greenhouse at +18 ° C. Six days after infection, fungal attack was examined.

The compounds in Tables 1-20 showed good activity for this test.

Example B-7: Botrytis cinerea (Grape botrytis)

It was treated with 5 major grape plant cultivar (cv.) The test compound (0.02% active substance) formulated to obtain tedel (Gutedel) in a spray chamber. Two days after application, the plants were inoculated by spraying a spore suspension ( ^1.5 × 10 ⁵ conidia / ml) onto the test plants. After incubation at + 21 ° C. and 95% relative humidity for 3 days in a greenhouse, disease development was examined.

The compounds in Tables 1-20 showed good activity for this test.

At the indicated concentrations, compounds 1.002, 1.002 *, 1.003, 1.024 and 7.002 showed over 70% fungal infection control in this test.

Example B-8: Botrytis cinerea Effects on / tomatoes (tomato botrytis)

Four main tomato plant varieties (cv.) Roter Gnom were treated with test compounds formulated in a spray chamber (0.02% active material). Two days after application, the tomato plants were inoculated by spraying a spore suspension (1 × 10 ⁵ conidia / ml) onto the test plants. After incubation at + 20 ° C. and 95% relative humidity for 4 days in a greenhouse, disease development was examined.

The compounds in Tables 1-20 showed good activity for this test.

At the indicated concentrations, compounds 1.002, 1.002 *, 1.017, 1.024 and 7.002 showed over 70% fungal infection control in this test.

Example B-9: Pyricularia oryzae Effect on Rice / Rice (Rice blast)

Three main rice plant varieties (cv.) Sasanishiki were treated with test compounds formulated in a spray chamber (0.02% active material). Two days after application, rice plants were inoculated by spraying a spore suspension (1 × 10 ⁵ conidia / ml) onto the test plants. After incubation at + 25 ° C. and 95% relative humidity for 6 days, disease development was examined.

The compounds in Tables 1-20 showed good activity for this test.

At the indicated concentrations, compounds 1.024 and 7.002 demonstrated over 70% fungal infection control in this test.

Example B-10: Pyrenophora teres (Helminthosporium) Effects on barley / barley (net blotch

1 was treated with the main varieties of barley plants (cv.) The test compound (0.02% active substance) formulated the Regina (Regina) in a spray chamber. Two days after application, barley plants were inoculated by spraying a spore suspension (3 × 10 ⁴ conidia / ml) onto the test plants. After incubation at + 20 ° C. and 95% relative humidity for 2 days, disease development was examined.

The compounds in Tables 1-20 showed good activity for this test.

At the indicated concentrations, compounds 1.001, 1.002, 1.002 *, 1.003, 1.004, 1.017, 1.023, 1.024, 1.079, 1.275, 3.002, 6.002 and 7.002 showed over 70% fungal infection control effects in this test.

Example B-11: Fusarium culmorum Effect on wheat / wheat (wheat fusarium head blight)

A conidia suspension of F. culmorum (7 × 10 ⁵ conidia / ml) was mixed with the formulated test compound (0.002% active material). The mixture was previously applied to a pouch with filter paper. After application, wheat seeds (cv. Oretis ) were sown in the upper fault of the filter paper. Next, the prepared pouches were incubated for 11 days with a light period of 14 hours at a temperature of about + 10 ° C to + 18 ° C and 100% relative humidity. The extent of disease development was examined in the form of brown lesions on the roots.

The compounds in Tables 1-20 showed good activity for this test.

At the indicated concentrations, compounds 1.002, 1.004, 1.005 and 7.002 showed over 70% fungal infection control in this test.

Example B-12: Septoria nodorum Effects on wheat / septia leaf spot of wheat

1 was treated with the main varieties of wheat plants (cv.) The test compound (0.02% active substance) formulated in the arena (Arina) in a spray chamber. One day after application, wheat plants were inoculated by spraying a spore suspension ( ⁶ × 10 ⁵ conidia / ml) onto the test plants. After 1 day incubation at + 22 ° C. and 95% relative humidity, the plants were stored in a greenhouse for 7 days at + 22 ° C. and 60% relative humidity. Disease development was examined 8 days after inoculation.

The compounds in Tables 1-20 showed good activity for this test.

At the indicated concentrations, compounds 1.002, 1.002 *, 1.003, 1.004, 1.017, 1.024, 1.079, 1.080, 1.260, 1.275, 3.002, 6.002, 10.002, 9.002, 14.002, 15.002 and 7.002 were more than 70% fungal infections in this test. Control effect was shown.

Claims (15)

Compound of Formula I or salt thereof: (I) The sum of (m + p) in the formula is 0, 1, 2 or 3; n and q are each independently 0 or 1 and the sum of (m + p + q) is 1, 2, 3 or 4; R ₁ is hydrogen, halogen, alkoxy, haloalkyl, haloalkoxy or alkyl; R ₂ is hydrogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -haloalkyl or C ₁ -C ₆ -alkoxy; R _2A is hydrogen, C ₁ -C ₆ -alkyl, C ₃ -C ₄ -alkenyl or C ₃ -C ₄ -alkynyl; R ₃ , R ₄ , R ₅ and R ₆ are each independently of the other hydrogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -haloalkyl, hydroxy-C ₁ -C ₆ -alkyl or C _1- C ₆ -alkoxy-C ₁ -C ₆ -alkyl, or cyclic members CR ₃ R ₄ or CR ₅ R ₆ or CR ₂ R _2A are each independently a carbonyl group (C═O) or a C═S group; X is C═O, C═S, S═O, or O═S═O; Y is O, S, C═O, CH ₂ , —N (R ₈ ) —, —ON (R ₈ ) —, —N (R ₈ ) —O— or —NH—; R ₇ is hydrogen, C ₁ -C ₄ -alkyl, C ₃ -C ₄ -alkenyl, C ₃ -C ₄ -alkynyl, -CH ₂ OR ₈ , CH ₂ SR ₈ , -C (O) R ₈ , -C (O) OR ₈ , SO ₂ R ₈ , SOR ₈ or SR ₈ ; And R ₈ is C ₁ -C ₈ -alkyl, C ₁ -C ₈ -alkoxyalkyl, C ₁ -C ₈ -haloalkyl or phenyl C ₁ -C ₂ -alkyl, wherein the phenyl is halo or C ₁ -C ₄ It may be substituted with up to 3 groups selected from -alkyl. According to claim 1, wherein the site Is N-oxazolidin-2-one, N-oxazolidine-2-thione, N- [1,2,3] oxathiazolidine-2-oxide, N- [1,2,3] oxathia Zolidine-2,2-dioxide, N-pyrrolidin-2-one, N-pyrrolidine-2-thione, N-pyrrolidine-2,5-dione, N-thiazolidin-2-one , N-4-methylene-oxazolidin-2-one, N-piperidine-2,6-dione, N-morpholine-2,3-dione, N-morpholine-2,5-dione, N -Imidazolidin-2-one, N- [1,2,4] -oxazolidin-5-one, N- [1,2,4] -oxazolidin-3-one, N- [1 , 2,5] -oxadiazin-6-one, N- [1,2,4] -oxadiazin-3-one, azepan-2-one or [1,3] oxazinan-2-one A compound characterized by representing a ring system selected from: A compound according to claim 1 or 2, wherein R ₁ is chloro, fluoro, trifluoromethyl, trifluoromethoxy or 1,1,2,2-tetrafluoroethoxy. 4. The compound of claim 1, wherein R ₂ is hydrogen, methyl, trifluoromethyl, or ethyl and R _2A is hydrogen or methyl. 5. The compound according to any one of claims 1 to 4, wherein R ₇ is hydrogen, methyl, ethyl, allyl, propargyl, methoxymethyl, thiomethoxymethyl or ethoxymethyl. . 6. The compound of claim 1, wherein X is carbonyl, C = S, or S═O, Y is oxygen, and R ₃ , R ₄ , R ₅ and R ₆ are independently hydrogen. Or methyl. The compound of claim ₁ , wherein R ₁ is chloro, fluoro, trifluoromethyl, trifluoromethoxy or 1,1,2,2-tetrafluoroethoxy; R ₂ is hydrogen, methyl, trifluoromethyl or ethyl; R _2A is hydrogen or methyl; R ₅ and R ₆ are independently of each other hydrogen, methyl, hydroxymethyl, hydroxyethyl or methoxyethyl; R ₇ is hydrogen, methyl, ethyl, allyl, propargyl, or methoxymethyl; X is carbonyl, C = S, or S═O, Y is oxygen, sulfur, —ON (CH ₃ ) —, or —N (CH ₃ ) —O—; m and n are 0 and p and q are each 1. 8. The compound of claim ₁ , wherein R ₁ is chloro; R ₂ is methyl or trifluoromethyl; R _2A is hydrogen or methyl; One of R ₅ and R ₆ is hydrogen or methyl and the other is hydrogen, methyl, hydroxymethyl, hydroxyethyl or methoxyethyl; R ₇ is hydrogen or methoxymethyl; X is carbonyl and Y is oxygen; m and n are 0 and p and q are each 1. The compound of claim ₁ , wherein R ₁ is chloro; R ₂ is methyl; R _2A is hydrogen; R ₅ and R ₆ are independently of each other hydrogen or methyl; R ₇ is hydrogen or methoxymethyl; X is carbonyl; Y is oxygen; m and n are 0 and p and q are each 1. The compound of claim 1, wherein 3- {4- [2- (3-chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2yl} -oxazolidin-2-one, N- {4- [2- (3-Chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -pyrrolidin-2-one, (3-Chloro-phenyl)-{4- [2- (2-oxo- [1 2,3] oxathiazolidin-3-yl) -pyridin-4-yl] -pyrimidin-2-yl}- Amine, 3- {4- [2- (3-fluoro-phenylamino) -pyrimidin-4yl] -pyridin-2-yl} -4-methyl-oxazolidin-2-one, 3- {4- [2- (3-trifluoromethyl-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -4-methyl-oxazolidin-2-one, (3-Chloro-phenyl)-{4- [2- (4-methyl-2-oxo- [1,2,3] oxathiazolidin-3-yl) -pyridin-4-yl] -pyrimidine- 2-yl} -amine, 1- {4- [2- (3-Chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -5-methyl-pyrrolidin-2-one, 3- {4- [2- (3-chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -4-ethyl-oxazolidin-2-one, 3- {4- [2- (3-chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -4-n-propyl-oxazolidin-2-one, 3- {4- [2- (3-chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -4-i-propyl-oxazolidin-2-one, 3- {4- [2- (3-Chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -5-methyl-oxazolidin-2-one, 3- {4- [2- (3-Chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -4-methyl-oxazolidin-2-one, 3- {4- [2- (3-chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -4-methyl-oxazolidine-2-thione, (S) -3- {4- [2- (3-chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -4-methyl-oxazolidin-2-one, 3- {4- [2- (3-chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -4-trifluoromethyl-oxazolidin-2-one, (R) -3- {4- [2- (3-chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -4-methyl-oxazolidin-2-one, 3- {4- [2- (3-Chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -4-trifluoromethyl- [1,3] oxazinan-2-one , 3- {4- [2- (3-chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -4-methyl- [1,3] oxazinan-2-one, 1- {4- [2- (3-Chloro-phenylamino) -pyrimidin-4-yl] -pyridin-2-yl} -5-trifluoromethyl-pyrrolidin-2-one, and 3- (4- {2-[(3-Chloro-phenyl) -methoxymethyl-amino] -pyrimidin-4-yl} -pyridin-2-yl) -4-methyl-oxazolidin-2-one Compound selected from the group comprising. a) U is a leaving group and the other moiety represents a compound of Formula II (or a salt thereof) having the meaning given to the compound of Formula I; (II) R ₂ to R ₆ , R _2A , X, Y, m, p and q are cyclic amine ring systems (or salts thereof) of formula III having the meanings given for compounds of formula I (III) And reacting in the presence of a catalyst such as palladium or in the presence of a base, or b) R ₁ to R ₇ , R _2A , X, Y, n, m, p and q have the meaning given for the compound of formula I and U ′ represents a compound of formula IV wherein (IV) Optionally cyclizing by heating in the presence of a base, or c) q is 1 and R ₁ , R ₂ , R _2A , R ₅ , R ₆ , R ₇ , Y, n and p are compounds of formula V having the meanings given for compounds of formula I (V) Reacted with phosgene, di- or triphosgen, carbonyldiimidazole, thiophosgene, thiocarbonyldiimidazole or thionylchloride, where X is C = O, C = S or S = O, q is 1, Compounds of subformula Ia wherein R ₁ , R ₂ , R _2A , R ₅ , R ₆ , R ₇ , Y, n and p have the meaning given to the compound of formula I (Ia) To obtain, or d) R ₁ to R ₇ , R _2A , Y, n, m, p and q are compounds of corrosion Ib having the meanings given for the compound of formula I; (Ib) Oxidizing with an oxidizing amount of NaIO ₄ / RuCl ₃ , NaOCl / RuO ₂ or KMnO ₄ to form a compound of formula I wherein X is O = S = O, or e) a compound of Formula VI wherein R ₁ to R ₇ , R _2A , Y, n, m, p and q have the meanings given for the compound of Formula I; . (VI) A method for preparing a compound according to claim 1 comprising reacting with an oxidized amount of iodine to form a compound of formula I wherein X is S═O. A composition for controlling and preventing phytopathogenic microorganisms comprising the compound of formula I according to claim 1 as an active ingredient with a suitable carrier. Use of a compound of formula I according to claim 1 to protect plants against infection by phytopathogenic microorganisms. A method for controlling and preventing infection of crop plants by phytopathogenic microorganisms, comprising applying a compound of formula I according to claim 1 as an active ingredient to a plant, part of the plant or a locus thereof. The method of claim 13, wherein the phytopathogenic microorganism is a fungal organism.